Formation of corrosion resistant plasma electrolytic oxidation coatings on aluminium alloy with addition of sodium tungstate species

Plasma electrolytic oxidation (PEO) coatings were formed in silicate based electrolytes without and with the addition of sodium tungstate on AA?6063 aluminium alloy. Microstructure, composition and corrosion resistance of PEO coatings were investigated by scanning electron microscopy, X-ray diffraction and electrochemical impedance spectroscopy and potentiodynamic polarisation test respectively. The effects of additive sodium tungstate were examined. The results showed that the additive containing PEO coatings were of dense structure with additional phase (WO₃) and of less cracks than the additive free PEO coating. In addition, additive containing coatings were of better corrosion resistance than the additive free PEO coating, which was confirmed by electrochemical impedance spectroscopy and potentiodynamic polarisation tests. Furthermore, long time immersion test revealed that the PEO coated alloy with the addition of 12?g?L^??1 sodium tungstate maintained high impedance over 82?h in 3.5?wt-%NaCl, while the PEO coating without additive was unable to protect the substrate after such long time immersion.     

Characterization and corrosion studies of fluoride conversion coating on degradable Mg implants

Fluoride conversion coating was synthesized on magnesium (Mg) by immersion treatment in hydrofluoric acid (HF) at room temperature, with the aim of improving the corrosion resistance of Mg in applications as degradable implant material. After an immersion period of 24 h in 48% HF, the samples carried a bronze color, and the conversion coating was dense and free of cracks. Field-emission scanning-electron microscopy (FE-SEM) of the cross-section revealed a coating thickness of about 1.5 μm. Atomic-force microscopy (AFM) recorded an average surface roughness of ∼ 21 nm for the coated sample, similar to that of the untreated one (∼ 17 nm). The coating was mainly composed of magnesium fluoride (MgF₂) as identified by thin-film X-ray diffractometry (TF-XRD), consistent with compositional analysis using X-ray photoelectron spectroscopy (XPS). The MgF₂ was in the form of crystallites of a few nm. A small amount of oxygen was present inside the coating, suggesting that some F⁻ ions are replaced by hydroxyl (OH⁻) ions in the MgF₂ structure, or that a small amount of Mg(OH)₂ was present. The corrosion resistance of untreated and conversion coated Mg in Hanks' solution was studied using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization tests, and immersion tests. EIS results showed a polarization resistance of 0.18 kΩ cm² for the untreated Mg and 5.2 kΩ cm² for the coated sample, giving an improvement of about 30 times. Polarization tests also recorded a reduction in corrosion current density from 400 μA/cm² to 10 μA/cm², showing an improvement of about 40 times. The galvanic effect between untreated and fluoride-coated Mg samples was small. Immersion tests in Hanks' solution also resulted in a much milder and more uniform corrosion damage on the fluoride-coated samples. The results of the present study showed that fluoride coating by conversion treatment is a simple and promising way of enhancing the corrosion resistance of Mg in Hanks' solution, or that it may be employed as a pretreatment step for subsequent coating.     

Effect of Ternary Elements on the Oxidation Behavior of Aluminized TiAl Alloys

The effects of ternary elements added to TiAl on the coating layer formed by the pack-aluminizing process was studied with respect to oxidation resistance and mechanical properties. All the TiAl specimens, with various amounts of Nb, Cr, Fe, and V, were pack aluminized under identical conditions using a high-activity process. Among the ternary alloying elements tested, Nb showed the best property of the TiAl₃ coating layer formed on the surface and, consequently, the best oxidation resistance. The TiAl₃ coating layer becomes thicker and has a finer grain size as the content of Nb or Cr is increased. Microhardness tests revealed that the addition of Nb or Cr improved the toughness of the coating layer and thus improved the cracking resistance. Cyclic oxidation tests showed that the TiAl₃ coating layer formed on the TiAl alloy has better oxidation resistance with increasing Nb content. The ductility and oxidation resistance of the TiAl₃ coating layers improved with Nb addition, which contributes to the grain refinement of TiAl₃. The Nb present in the TiAl₃ coating layer inhibits grain growth by the solute-drag effect and retards inward diffusion of Al to the TiAl matrix by forming (Nb, Ti)Al₃ precipitates during high-temperature oxidation.     

6061 铝合金表面无铬稀土镧转化膜性能的研究

利用极化曲线方法,研究了以La(NO3)3.6H2O为促进剂的磷酸盐转化膜的耐蚀性,同时与铬磷化膜及无稀土促进的单纯磷酸盐膜的耐蚀性进行了对比;通过划格法和全浸腐蚀试验,研究了这三种转化膜与有机涂层间的结合力。结果发现:与单纯磷酸盐膜相比,稀土促进生成的磷酸盐膜中的传输阻力增加,耐蚀性明显增强,而与铬磷化膜相比,二者在弱极化区的耐蚀性能相近;稀土促进生成的磷酸盐膜与有涂层间的结合力明显优于铬磷化膜。     

Conversion coating treatment for AZ91 magnesium alloys by a permanganate‐REMS bath

A permanganate‐rare earth metal salt (REMS) chemical conversion bath was applied to a sample of AZ91 magnesium alloy in this study, a red‐brown conversion coating formed subsequently on the sample surface. The test results of this coating with a scanning electron microscope (SEM) showed that there existed net‐like cracks on the surface of the treated magnesium alloy. With the analyses of X‐ray Diffraction (XRD) and X‐ray Photoelectron Spectroscopy (XPS), a further study of this coating indicated that the coating was structurally amorphous and mainly composed of CeO₂, MnO, MnO₂, MgO, Mg(OH)₂ and MgAl₂O₄. Furthermore, the electrochemical polarization tests showed that compared with the samples treated by the chrome‐based method, the open‐circuit potential of the magnesium alloy coated in permanganate‐REMS bath moved from ? 1.34 V_SCE to ? 1.28 V_SCE and the anodic current density of the alloy, at the same potential, decreased evidently in simulated sweat fluid. The cracks in the chemical conversion coating should be caused by the phase structure of the magnesium alloy. During the chemical conversion process, the localized corrosion micro‐cell led to the formation of the net‐like cracks on the surface. Simultaneously, the dehydration of the surface coating after treatment also accelerated the formation of the cracks at the coating surface.     

Ni/Cu定向结构涂层在不同浓度H2SO4中的耐蚀性能

为了研究Cu元素对Ni基合金定向结构涂层耐腐蚀性能的影响,向Ni60合金粉末中添加了5%Cu(质量分数,下同),制备了定向结构Ni60/Cu复合涂层。采用电化学试验和浸泡试验,评估了涂层在不同浓度H₂SO₄溶液中的电化学腐蚀特性和浸泡腐蚀性能,探讨了涂层在不同浓度H₂SO₄溶液中的腐蚀行为。结果表明,涂层在不同浓度H₂SO₄溶液中的腐蚀均表现为活化-钝化-过钝化的过程,电化学阻抗谱在整个时间常数内具有典型的容抗特征,H₂SO₄溶液浓度从5%增至80%时,电荷转移电阻先减小后增大,涂层的耐腐蚀性呈现先降低后升高的趋势。随着H₂SO₄溶液浓度的增加,涂层表面的腐蚀程度先加剧后逐渐减缓,且在H₂SO₄溶液浓度为40%时,腐蚀电位移至最负,腐蚀电流密度增至最大。但在H₂SO₄溶液浓度达到80...     

Preparation and cytocompatibility of Si-incorporated nanostructured TiO2 coating

Silicon (Si)-incorporated TiO₂ coating with porous and nanostructured surface on titanium was prepared by plasma electrolytic oxidation (PEO). The microstructure, phase composition and elemental distribution of the coating were characterized using scanning electron microscopy, X-ray diffraction and energy-dispersive X-ray spectrometry. MG63 cells were cultured on the surface of the coating to investigate its cytocompatibility. Potentiodynamic polarization tests were used to measure its corrosion resistance. The results showed that Si was successfully incorporated and distributed homogeneously in the coating. The Si-incorporated coating showed a denser and finer coating structure and higher MG63 cell proliferation rate and vitality than Si-free coating. The corrosion resistance of the Si-incorporated coating was also significantly improved. In conclusion, it is an interesting and promising way to regulate the functions of the coatings by introducing desired elements, such as Si, by PEO technique.     

Microstructure and corrosion resistance of ceramic coating on carbon steel prepared by plasma electrolytic oxidation

Ceramic coating was prepared on Q235 carbon steel by plasma electrolytic oxidation (PEO). The microstructure of the coating including phase composition, surface and cross-section morphology were studied by X-ray diffraction (XRD), Fourier transform infrared spectroscope (FTIR) and scanning electron microscopy (SEM). The corrosion behavior of the coating was evaluated in 3.5% NaCl solution through electrochemical impedance spectra (EIS), potentiodynamic polarization and open-circuit potential (OCP) techniques. The bonding strength between Q235 carbon steel substrate and the ceramic coating was also tested. The results indicated that PEO coating is a composite coating composed of FeAl₂O₄ and Fe₃O_4. The coating surface is porous and the thickness is about 100 μm. The bonding strength of the coating is about 19 MPa. The corrosion tests showed that the corrosion resistance of Q235 carbon steel could be greatly improved with FeAl₂O₄-Fe₃O₄ composite coating on its surface.     

Ti6Al4V钛合金表面Al2O3颗粒改性微弧氧化涂层制备及性能

微弧氧化技术是一门新的表面处理技术,在很多领域有着广泛的应用前景,但其结构受限于电解液成分。本文通过在磷酸盐电解液中加入Al2O3陶瓷颗粒,使得在Ti6Al4V钛合金表面的微弧氧化涂层结构和性能得到改性。涂层的结构和性能通过扫描电镜和XRD衍射仪进行表征和测试,涂层的抗高温氧化性能和热震性能通过高温热循环氧化试验和热震试验进行测试。结果表明,通过在电解液中添加Al2O3陶瓷颗粒,涂层由Al2TiO5 and TiO2组成,涂层更为致密,表现出更为优异的抗高温氧化和热震性能。电解液中游动的Al2O3陶瓷颗粒在微弧氧化过程中被吸入到样品表面并进入涂层,涂层的结构和性能得到改性。     

Effect on Corrosion Resistance of Ce-Rich-Sealed Ni-P Coatings on Cf/Al Composite Surface

In this study, Ni-P coatings and sealing of the coatings by Ce-rich solution on Cf/Al composite surface for enhanced corrosion resistance are investigated. The corrosion resistance of uncoating sample in 3.5 wt.% NaCl solution was investigated and a comparison with Ni-P and Ce-sealed Ni-P coatings is given. Effect of Ce-sealing on Ni-P coating is discussed. The results of electrochemical measurements of corrosion performance of Cf/Al composites show that sealing of Ni-P coatings with Ce-rich solution can improve the corrosion resistance. The Ce-rich-sealed Ni-P coating has higher corrosion resistance than the coating without Ce, and the electroless plated Ni-P coating on composite surface has higher corrosion resistance than the bare sample, as evidenced by EIS and potentiodynamic polarization measurements. The microstructure of the Cf/Al composites and the two kinds of coatings (i.e., Ni-P coating and Ce-sealed Ni-P coating) were examined by scanning electron microscopy, energy dispersive spectroscopy, and transmission electron microscopy. The Ce-sealed Ni-P coatings on Cf/Al composite surface have a total thickness of ~11 μm of which 10 μm is the thickness of the Ni-P coating and ~1 μm is the thickness of the Ce-rich sealing. It shows that the selected area electron diffraction ring pattern of Ce-rich sealing on Ni-P plated composite is consistent with Ce₆O₁₁ or CeO₂. X-ray photoelectron spectroscopy results show that Ce⁴⁺ was the dominant oxidation state for Ce-rich sealing on Ni-P plated composite. The Ce-sealing treatment on Ni-P coating has improved the corrosion resistance over and above the corrosion resistance offered by the Ni-P mono-coating to the bare substrate.     

Structure and corrosion resistance of ZrO2 ceramic coatings on AZ91D Mg alloys by plasma electrolytic oxidation

The aim of this work is to study the structure and the corrosion resistance of the plasma electrolytic oxidation ZrO₂ ceramic coatings on Mg alloys. The ceramic coatings were prepared on AZ91D Mg alloy in Na₅P₃O₁₀ and K₂ZrF₆ solution by pulsed single-polar plasma electrolytic oxidation (PEO). The phase composition, morphology and element distribution in the coating were investigated by X-ray diffractometry, scanning electron microscopy and energy distribution spectroscopy, respectively. The results show that the coating thickness and surface roughness were increased with the increase of the reaction time. The ceramic coatings were of double-layer structure with the loose and porous outer layer and the compact inner layer. And the coating was composed of P, Zr, Mg and K, of which P and Zr were the main elements in the coating. P in the coating existed in the form of amorphous state, while Zr crystallized in the form of t-ZrO₂ and a little c-ZrO₂ in the coating. Electrochemical impedance spectra (EIS) and the polarizing curve tests of the coatings were measured through CHI604 electrochemical analyzer in 3.5% NaCl solution to evaluate the corrosion resistance. The polarization resistance obtained from the equivalent circuit of the EIS was consistent with the results of the polarizing curves tests.     

MoSi2 oxidation resistance coatings for Mo5Si3/MoSi2 composites

In order to improve the oxidation resistance properties of 30 at.% Mo₅Si₃/MoSi₂ composite at high temperature in air, a molybdenum disilicide coating was prepared on its surface by a molten salt technology. XRD and SEM analysis showed that only tetragonal MoSi₂ phase existed in the coating after being siliconized for 5 h at 900°C. The oxidation film formed on the uncoated sample was not dense, so that oxygen diffused easily through it. The volatilization of MoO₃ resulted in the oxidation film separating from the substrate. The MoSi₂ coating was proved to be an effective method to prevent 30 at.% Mo₅Si₃/MoSi₂ composites from being oxidized at 1200°C. A dense glassy SiO₂ film was formed on the MoSi₂ coating surface, which acted as a barrier layer for the diffusion of oxygen atoms to the substrate. The 30at.% Mo₅Si₃/MoSi₂ composites with a MoSi₂ coating showed much better oxidation resistance at high temperature.     

Corrosion resistance of the electro-galvanized steel treated in a titanium conversion solution

The conversion coating can be obtained by using a solution containing titanium tetrachloride, fluorosilicate acid and nitric acid. The results of X-ray photoelectron spectroscopy (XPS) showed that the titanium conversion coating consisted of ZnO, TiO₂ and Zn₄Si₂O₇(OH)₂. The formation process of the titanium conversion coating was studied. Effects of the immersion time, pH value and solution temperature on the corrosion resistance and the chemical composition of the titanium conversion coating were investigated by the salt spray test (SST) and XPS, respectively. The results of XPS and SST showed that the titanium conversion coating displayed better corrosion resistance with higher contents of Si and Ti. Results of corrosion tests (the salt spray and electrochemical test) indicate that the corrosion resistance of the conversion coating by titanium solution is better than that of the conversion coating using the traditional chromate solution.     

碳钢表面防腐超疏水TiO_2/PDMS涂层的制备及性能

针对碳钢腐蚀电位相对更负、更容易发生腐蚀的特点,在Q235钢表面制备超疏水TiO_2/PDMS涂层以提高其耐蚀性能。采用表面活性剂分散纳米TiO_2并进行改性,然后与PDMS混合,用溶胶凝胶法在Q235钢表面制备有聚二甲基硅氧烷(PDMS)过渡层的TiO_2/PDMS超疏水涂层。借助扫描电镜(SEM)、接触角测量仪、红外光谱(FT-IR)及X射线衍射仪(XRD)表征其表面涂层的表面形貌、化学成分及疏水性能,用电化学试验和浸泡试验测试其防腐性。结果表明:TiO_2/PDMS涂层表面具有独特的微纳结构,与水的接触角达到154.3°;其腐蚀电位由碳钢的-0.77 mV正移至超疏水涂层的-0.24 mV,腐蚀电流密度则下降两个数量级,即从5.02×10~(-6)A·cm~(-2)下降至3.95×10~(-8)A·cm~(-2);超疏水涂层的交流阻抗值高于碳钢基底3个数量级。经过7 d的3.5wt.%NaCl溶液浸泡,超疏水涂层并未发生失重。制备的TiO_2/PDMS超疏水涂层具有超疏水效果和良好的长期耐腐蚀性。     

Electroless Ni-P-PTFE-Al2O3 Dispersion Nanocomposite Coating for Corrosion and Wear Resistance

With the aim to produce a coating having good corrosion and wear resistance alongside hardness but lesser friction coefficient, Ni-P-PTFE-Al₂O₃ (NiPPA) dispersion coating was developed. This was achieved by introducing nanosized polytetrafluoroethylene (PTFE) and alumina (Al₂O₃) in the Ni-P matrix deposited on mild steel substrate. The coating was characterized using scanning electron microscopy, energy dispersive analysis of x-ray, and x-ray diffractrometry. Microhardness and wear resistance of the coating was measured using Vicker’s hardness tester and Pin-on-Disc method, respectively. The corrosion behavior was measured using electrochemical polarization and immersion tests with and without exposure in 3.5% NaCl solution. It is observed that codeposition of Al₂O₃ and PTFE particles with Ni-P coating results in comparatively smooth surface with nodular grains. The NiPPA coating was observed to have moderate hardness between electroless Ni-P-PTFE and Ni-P-Al₂O₃ coating and good wear resistance with lubricating effect. Addition of both PTFE and Al₂O₃ is observed to enhance corrosion resistance of the Ni-P coating. However, improvement in corrosion resistance is more due to addition of Al₂O₃ than PTFE. Continuous exposure for 10-20 days in corrosive solution is found to deteriorate corrosion protection properties of the coating.     

Formation of Ni-aluminide Coating Containing Hf by Molten-Salt Electrodeposition and Cyclic-Oxidation Resistance

The formation of a coating layer consisting of Ni-aluminide containing Hf on a Ni–10at.%Cr–8at.%Al alloy substrate was attempted by the electrodeposition of Hf, Ni, and Al. The cyclic-oxidation resistance for the alloy covered with this coating was then evaluated in air at 1,423 K. Ni was deposited by aqueous solution electrolysis. Hf and Al were deposited by molten-salt electrolysis. For the sample first treated with the Hf-deposition, subsequently treated with the Ni-deposition, followed by Al-deposition, a coating consisting of Ni₂Al₃ of about 40-μm thickness was uniformly formed on the alloy. At the center region of this coating, a Hf-concentration layer was formed. The cyclic-oxidation test showed that, for the untreated sample and the sample with only Ni and Al depositions, a mass reduction due to spallation of a scale took place during the initial oxidation period. On the contrary, for the sample with Hf, Ni, and Al depositions, a mass reduction due to spallation of a scale scarcely took place. The cross-sectional observation using SEM showed that, for the sample with Hf, Ni, and Al depositions after the oxidation test, an adhesive scale having a spiked shape was formed. This scale mainly consisted of α-Al₂O₃, and contained HfO₂ particles. It was postulated that, for this sample, the Hf in the Hf-concentration layer diffused into the surface region of the Ni-aluminide layer, contributing to improvement in the exfoliation resistance of the scale.     

Inclined impact–sliding wear tests of TiN/Al2O3/TiCN coatings on cemented carbide substrates

A chemical vapor deposition (CVD) TiN/Al₂O₃/TiCN coating has been commercially used as a protective coating on cemented carbide cutting tools to improve tool life and superficial quality of the workpiece. However, the CVD coating is relatively brittle and could fail due to fatigue cracking induced wear under localized contact stresses during the milling operation. Traditional coating evaluation techniques such as tribo tests, scratch tests and impact tests only involve single movement, i.e., either sliding or impacting. In the present work, the fatigue and wear behavior of the triple-layered coatings on cemented carbide substrates was investigated using a novel impact–sliding wear tester, which simulates a repetitive movement of combined impact and sliding motions between cutting tools and workpieces during interrupted milling operations. The coatings on the surface and cross-section were studied using Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray (EDX) analysis. The results from the impact component showed that fatigue cracking increased for the coating on a harder substrate likely due to the lower toughness of the substrate. The results from the sliding component showed that the wear resistance of the coating decreased as the substrate was softer. The test results provided constructive knowledge in selection and development of coatings for impact and sliding involved applications.     

The effects of 8-hydroxyquinoline on corrosion performance of a Mg-rich coating on AZ91D magnesium alloy

A Mg-HQ-rich primer was prepared by adding 45% pure magnesium particles and 5% 8-hydroxyquinoline in epoxy coating. The Mg-HQ-rich primer showed obviously better protection for AZ91D alloy than 50% Mg-rich primer. The additive 8-HQ combines with Mg²⁺ in the coating, forming a insoluble complex, MgQ₂, instead of Mg(OH)₂ on Mg particles. The MgQ₂ layer may retard dissolution of magnesium particles and prolong the cathodic protection effect of Mg-HQ-rich primer. Additionally, the corrosion products may also block the defects in the primer and the active sites on the substrate surface, thereby further increase the corrosion resistance of the Mg-HQ-rich primer.     

An investigation on oxidation,hot corrosion and mechanical properties of plasma-sprayed conventional and nanostructured YSZ coatings

Conventional and nanostructured YSZ coatings were deposited on IN-738 Ni super alloy by atmospheric plasma spray technique. The oxidation was measured at 1100 °C and hot corrosion resistance of the coating was measured in a mixed salt of V₂O₅ and Na₂SO₄ at 1050 °C using an atmospheric electrical furnace. According to the experimental results, nanostructured coatings showed a better oxidation and hot corrosion resistance than conventional one. The improved oxidation resistance of the nanocoating could be explained by the change of structure to a dense and more packed structure in this coating. The improvement in hot corrosion resistance was not as good as the oxidation but much better than conventional coating. The thermo-mechanical properties of the coating were tested using thermal cycles, nanoindentation, and bond strength tests during which nanostructured YSZ coating again showed a better performance by structural stability.     

High Temperature Performance of an FeAl Laser Coated 9Cr1Mo Steel

The isothermal high temperature corrosion behavior of an FeAl coating, coated on 9Cr1Mo steel through laser surface alloying, was studied in atmospheres of pure oxygen and O₂ + 1 %SO₂. The specimens were tested at 500, 600 and 700 °C for 4–100 h. The mass change of the specimens versus time of exposure was used to study the kinetics of oxidation. The coating degradation through interdiffusion of alloying elements between the surface layer and substrate was investigated by long-term oxidation tests in air. OM, SEM, FESEM, EDS and EPMA analyses were used to study the oxidation behavior of the intermetallic coating. The results showed excellent oxidation/sulfidation resistance of the coated material due to a negligible growth rate of the oxide scale. However, the coating was degraded because of the interdiffusion of Al and Fe atoms between the coating and substrate after prolonged exposure to elevated temperatures.